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Publication numberUS3045051 A
Publication typeGrant
Publication dateJul 17, 1962
Filing dateDec 21, 1959
Priority dateDec 21, 1959
Publication numberUS 3045051 A, US 3045051A, US-A-3045051, US3045051 A, US3045051A
InventorsJames G Coma, Virgil G Gerttula
Original AssigneeCrown Zellerbach Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Production of dialkyl sulfoxides
US 3045051 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

ing sulfoxides.

BfiiSfiSl V Patented July 17, 1962 7 3,045,051 rnonncrroN or DKALKYL SULFGXIDES James G. Coma and Virgil G. Gerttula, Vancouver,

Wash, assignors to Crown Zelierhach Corporation, San Francisco, Calii, a corporation of Nevada No Drawing. Filed Dec. 21, 1959, Ser. No. 866,741

13 Claims. (Cl. 260-407) thereof in liquid phase in the presence of a catalytic amount of a nitrogen oxide or concentrated nitric acid.

Several methods for the oxidation of organic sulfides to the corresponding sulfoxides have been described. Oxidatio'ns of dialkyl sulfides in the vapor phase with an oxygen-containing gas in the presence of a catalytic amount of a nitrogen gas have been disclosed by Smedslund in U.S. Patent Nos. 2,581,050 and 2,825,744. In these processes the sulfide is converted into the gaseous form prior to its conversion into the sulioxide, which process requires a relatively high temperature of the reaction and is difificult to carry out commercially due to large volumes of reactants which have to be handled. Furthermore, relatively large losses of nitric oxide employed as a catalyst occur during condensation of the reaction products due to the solubility of nitric oxide in the condensation product containing a mixture of a dialkyl sulfide and sulfoxide. US. Patent No. 2,825,745 (Smedslund) relates to a method for the manufacture of sulfoxides from the corresponding sulfides in either the liquid or thevapor phase. The latter method includes removal of moisture from the reactants, and particularly from atmospheric air which is used as the oxidizing medium in order to improve the yields of the result- "due to highly exothermic oxidation reaction. Moreover,

the reaction rate per unit volume ofvthe reactor is relatively low and the consumption of the nitric oxide'catalyst is relatively high. All of the foregoing processes 'are characterized by the fact that the entire volume of oxygen or oxygen-containing gas required for the conversion of the sulfide to the corresponding sulfoxide is introduced at the initial stage of the reaction. As mentioned hereinabove, due to. a highly exothermic character of the'reaction' at the point of oxygen feed into the dialkyl sulfide, serious difficulties have been encountered in removing the heat of the reaction and maintaining the reaction temperature within the desirable limits. Furthermore, the rate of incorporation of the reactants must be limited by the heat'transfer capacity of the reactor adjacent to the point of addition of oxygen.

We have now discovered that the above mentioned disadvantages of the liquid phase oxidation methods of the prior art can be overcome by introducing only a portion of the amount of oxygen necessary for conversion of the dialkyl sulfides to the corresponding sulfoxides at the initial point of the reaction zone, and introducing the remaining portion of oxygen into at least one other point In US. Patent No. 2,702,824 .(Wetten of the reaction zone during the passage of the reaction mixture through said zone.

It is, therefore, the general object of the present in vent-ion to provide an economical and commercially attractive process for the production of dialkyl sulfoxides from the corresponding sulfides in the liquid phase using oxygen or air as the oxidizing agent in the presence of a small catalytic amount of an oxygen-transmitting nitrogen oxide or concentrated nitric acid by incorporating the oxygen gas at multiple points in the reaction zone.

A further object of the present invention is to provide an improved process for the production of dialkyl sulfoxides in the liquid phase, which process is safe and convenient to operate and in which the reaction rate per unit volume of the reactor is significantly increased while the amount of the nitrogen oxide catalyst employed is markedly reduced. 7

Other objects of this invention will be apparent to those skilled in the art from the following disclosure.

The essential characteristic of this invention lies in the provision of an improved step in the course of the oxidation of a dialkyl sulfide to the corresponding sulfoxide in the liquid phase, namely the introduction of oxygen or air at multiple points of the reaction zone, as compared to the prior art procedures wherein the entire amount of oxygen necessary for conversion of the sulfide to the sulfoxide is added at the initial point of the reaction Zone.

Generally stated, the herein described process of producing a dialkyl sulfoxide comprises introducing at the initial point of the reaction zone a liquid dialkyl sulfide, a catalyst selected from the group consisting of nitrogen oxides and concentrated nitric acid and a portion of the stoichiometric amount of oxygen necessary for conversion of the sulfide to the sulfoxide. Thereafter the remaining portion of the stoiohiometric amount of oxygen is introduced into at least one other point of the reaction zone, the latter point being longitudinally spaced from the initial point of the introduction of oxygen. After the entire amount of oxygen which isrequired for complete conversion of the sulfide to the sulfoxide has been introduccd, the resulting dialkyl sulfoxide is withdrawn at the opposite end of the reaction Zone. The vent gases containing primarily a reduced nitrogen oxide flow out at the same end of the reaction zone and may be recovered and recycled or otherwise disposed. The liquid dimethyl sulfoxide may be purified in order to remove a small amount of impurities, such as methane sulfonic acid and unreacted dialkyl sulfide. If desired, a portion of the purified dialkyl sulfoxide may be recycled and reintroduced intothe initial point of the reaction zone together with the catalyst.

It should therefore be emphasized that, Whereas the prior art processes are based on the incorporation of the entire amount of oxygen in the beginning of the oxidation reaction, the process of this invention is based on the amount of the catalyst required for the reaction is V substantially reduced. g

'The process of this invention is applicable to the oxidation of dialkyl sulfides having the formula R--S--R wherein R is an alkyl group containing up to 4 carbon atoms and R is the same or a different :alkyl group containing up to 18 carbon atoms. Such dialkyl sulfides include lower dialkyl sulfides, for example dimethyl sulfide,

diethyl sulfide, dipropyl sulfide, dibutyl sulfide, methyl ethyl sulfide, methyl butyl sulfide, methyl isopropyl sulfide; methyl-higher alkyl sulfides, for example methyl octyl sulfide, methyl octadecyl sulfide; as well as ethylbutyl sulfide, butyl octyl sulfide, etc.

The preferred oxidizing gas in accordance with the in vention is pure oxygen. However, air or a mixture of oxygen and air are satisfactory. The total amount of oxygen introduced into the reaction zone should be sufficient to effectuate a substantially complete conversion of the dialkyl sulfide to the corresponding sulfoxide in accordance with the stoiehiometry of the reaction.

The catalysts which may be used in the oxidation reaction of this invention include nitrogen oxides such as NO, N N 0 and N 0 as well as concentrated nitric acid preferably of at least 99% concentration. Due to the uniform nature of the reaction and the gradual conversion of the organic sulfide to the corresponding sulfoxide, the amount of the catalyst employed is substantially lower than that employed in the prior art processes including a single introduction of oxygen into the reaction zone.

For example, using the stepwise procedure of adding oxygen into four points of the reaction zone and introducing nitrogen dioxide in the amount of 1 mole of N0 per 20 moles of dimethyl sulfide, we have obtained a final reaction product containing 96% dimethyl sulfoxide. On the other hand, with an addition of oxygen at one point only at the bottom of the same reactor, a greater amount of N0 catalyst, namely 1 mole of N0 per moles of dimethyl sulfide, was required and the final reaction product contained no more than 92% of dimethyl sulfoxide.

The process of this invention may be carried out over a wide range of temperatures, e.g. from as low as above the freezing point of the liquid mixture up to about 60 C., preferably between 15 C. and 50 C. The conversion of the sulfide to the, corresponding sulfoxide occurs in a very short period of time and is substantially complete. The yields are very good, usually in excess of 95% of the theoretical value.

The following example is presented in order to illustrate but not to limit the scope of the present invention.

Dimethyl sulfide, a solution of nitrogen dioxide (N0 in recycled dimethyl sulfoxide and approximately onequarter of the stoichiometric amount of oxygen required for the conversion. of the sulfide to the sulfoxide are fed continuously at the bottom of a vertical reactor provided with pipes conveying a cooling liquid, such as water, and having about 22 square feet of heat transfer surface per cubic foot of reactor volume, which is adequate for removal of the heat of reaction. While the resulting liquid mixture is passed upwardly through the reaction zone, the remaining three-quarters of said stoiehiometric amount of oxygen are introduced successively in substantially equal proportions into three other longitudinally and equally spaced points above the point of initial introduction of oxygen into the reaction zone. The vent gases containing primarily reduced nitrogen oxide (NO) fiow 6 out at the top of the reactor, while the resulting liquid dimethyl sulfoxide is withdrawn from the reaction zone at a point adjacent the top of the reactor. The dimethyl sulfoxide may be purified, if desired, and a portion thereof may be recycled for the preparation of fresh nitrogen dioxide catalyst solution to be introduced at the bottom of the reactor. Similar procedure may be applied to the conversion of other dialkyl sulfides in conjunction with other catalysts, as set forth hereinabove.

The typical process conditions employed in conjunction with the present example are given in Table 1 hereinbelow together with the conditions applied to a prior art process wherein the entire stoichiometric amount of oxygen is incorporated at the initial point of the reaction zone.

Table 1 Present Prior Art Process Process Dimethyl Sulfide Reaction Rate, grams/hour 6, 950 1, 720 N02 Addition Rate, grams/hour 258 87 Amount of N0: Added Based On Dimethyl Sulfide, Percent 3. 72 5. 06 Volume of Reactor, cu. ft 0.673 0. 334 Reaction Temperature, 35-50 35-50 Reaction Rate, Lbs. Dimethyl Sulfide/hr./eu. it. of

Reactor 22. 70 11.35 Dimethyl sulfoxide Yield, Percent 96 92 process of the present invention offers several commercially significant advantages, as compared to that of the prior art, namely a double reaction rate per unit reaction volume, a decrease of about 27% in the amount of nitrogen dioxide catalyst consumed, a higher yield of dimethyl sulfoxide produced with the attendant substantially complete conversion of the dimethyl sulfide to the dimethyl sulfoxide.

The above-mentioned and other advantages of the present process greatly enhance the economic aspects of producing dimethyl sulfoxide and other dialkyl sulfoxides on a commercial scale. Dimethyl sulfoxide is potentially useful as a versatile solvent for various types of polymers and for certain gases, such as acetylene, as a softener and humectant for cellulosic materials, and as a freezing point depressant for water. Higher dialkyl sulfoxides prepared according to this invention may be used as surface-active agents, detergents and plasticizers.

It is to be understood that changes and modifications may be made in regard to specific details of the invention herein described which are intended to be included within the scope of the appended claims.

We claim:

1. In a process of producing a dialkyl sulfoxide from a corresponding sulfide by oxidation thereof in liquid phase which comprises reacting in a reaction zone a dialkyl sulfide with oxygen in the presence of a catalyst selected from the group consisting of nitrogen oxides and concentrated nitric acid and then Withdrawing the resulting sulfoxide from the reaction zone, the improvement which comprises introducing at the initial point of said reaction zone a portion of the stoichiometric amount of oxygen necessary for conversion of the sulfide to the suitoxide and introducing the remaining portion of the stoichiometrie amount of oxygen into at least one other point of said reaction zone to effect a substantially complete conversion of the sulfide to the sulfoxide.

2. The process of claim 1 wherein the dialkyl sulfide comprises a lower dialkyl sulfide.

3. The process of claim 1 wherein the dialkyl sulfide comprises a methyl-alkyl sulfide.

4. The process of claim 1 wherein the dialkyl sulfide comprises dimethyl sulfide.

- 5. The process of claim 1 wherein the catalyst comprises nitrogen dioxide.

6. The process of claim 1 wherein the oxidation is carried out at a temperature in excess of the freezing ggi ntcof the reaction mixture but not exceeding about 7. The process of claim 1 wherein the oxidation reaction is carried out between about 15 C. and 50 C.

8. The process of claim 1 wherein substantially equal portions of the stoichiometric amount of oxygen are introduced at four longitudinally and approximately equally spaced points of the reaction zone.

9. The process of claim 1 wherein the dialkyl sulfide, the catalyst and a pfiiortion of said stoiehiometric amount of oxygen are introduced at a point near the bottom of a vertical reaction column, the reaction mixture is passed upwardly, the remaining portion of said stoichiometric amount of oxygen is introduced into at least one other 5 point in the column above the point of the initial introduction of oxygen, and the resulting sulfoxide is withdrawn near the top of the reaction column.

10. In a process of producing dimethyl sulfoxide, by I oxidation of dimethyl sulfide in liquid phase in the pres- 5 ence of nitric dioxide catalyst, the improvement which comprises introducing the stoichiometric amount of oxygen necessary for conversion of the sulfide to the sulfoxide into at least two longitudinally spaced points of the reaction zone.

1 1 1. The process of claim 10 wherein substantially equal portions of the stoichiometric amount of oxygen are introduced at four longitudinally and approximately equally spaced points of the reaction zone.

12. The process of claim 10 wherein the oxidation of 15 dimethyl sulfide is carried out between about 15 C. and

References Cited in the file of this patent UNITED STATES PATENTS Marshall Oct. 6, 1953 2,702,741 Robertson Feb. 22, 1955 2,702,824 Wetterholm et al Feb. 22, 1955 2,797,151 Schnur et a1. June 25, 1957

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2654658 *Apr 2, 1948Oct 6, 1953Kellogg M W CoApparatus for nitration of organic compounds
US2702741 *Jul 19, 1951Feb 22, 1955Celanese CorpTower reactor
US2702824 *Aug 18, 1952Feb 22, 1955Nitroglycerin AbLiquid-vapor phase method for producing lower dialkyl sulfoxides
US2797151 *Jul 18, 1952Jun 25, 1957Ruhrchemie AgApparatus for producing nitric acid
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3243463 *Nov 14, 1962Mar 29, 1966Procter & GambleAlkyl sulfoxide detergent
US3247258 *Oct 25, 1961Apr 19, 1966Chevron ResMethyl-beta-hydroxyalkyl sulfoxides
US3256340 *May 13, 1963Jun 14, 1966Glen A RussellCondensation reactions in dimethyl sulfoxide solution and sulfoxides
US3257462 *Nov 14, 1962Jun 21, 1966Procter & GambleSulfoxide detergent compounds
US3288859 *Mar 30, 1965Nov 29, 1966Procter & GambleReactions of alkali metal salts of sulfinyl carbanions and alkanesulfenates with epoxy compounds and novel compounds derived therefrom
US3336233 *Sep 12, 1966Aug 15, 1967Procter & GambleBuilt detergent compositions containing 3-hydroxyalkyl alkyl sulfoxides
US3360369 *May 1, 1964Dec 26, 1967Dietzgen Co EugeneDiazotype reproduction material
US4362271 *Oct 29, 1980Dec 7, 1982Agence Nationale De Valorisation De La Recherche (Anvar)Procedure for the artificial modification of atmospheric precipitation as well as compounds with a dimethyl sulfoxide base for use in carrying out said procedure
US4446118 *May 27, 1982May 1, 1984Chevron Research CompanyScrubbing hydrogen sulfide from a fuel gas
US6414193 *Jan 28, 2000Jul 2, 2002Toray Fine Chemicals Co., Ltd.Continuously oxidizing dimethyl sulfide with gas mainly composed of oxygen obtained by pressure swing adsorption of air, using nox as catalyst in liquid phase, recycling solution containing dimethyl sulfoxide and nox to oxidation reaction
US6414194 *Apr 24, 2000Jul 2, 2002Gaylord Chemical CorporationPartially solidifying liquid phase comprising dimethyl sulfoxide and one or more impurities to form mixture comprising solid dimethyl sulfoxide and liquid residue, substantially separating solid from liquid residue
Classifications
U.S. Classification568/27
International ClassificationA01N41/10, C07C317/00
Cooperative ClassificationC07C317/00
European ClassificationC07C317/00